Fuel 303 (2021) 121255

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Chemical effects of anisole and toluene addition to n‑heptane on PAH

characteristics in laminar premixed flames by LIF measurement and
kinetic model
Yiran Zhang a, Anqi Jiao a, Youping Li a, Peng Liu b, Guofeng Yang a, Reggie Zhan a,
William L. Roberts b, Zhen Huang a, He Lin a, *
a
Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, China
b
Clean Combustion Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Anisole is a candidate renewable fuel that displays satisfying combustion characteristics, but its sooting char­
PAHs acteristics are not well known. The goal of this study is to investigate the chemical effects of anisole and toluene
Laminar premixed flames on PAH formation in n-heptane laminar premixed flames, using LIF measurement and chemical kinetic simu­
Anisole and toluene
lation. To focus on chemical effects, the equivalence ratios, dilution ratios, and flame temperatures were kept
LIF
Chemical effects
nearly unchanged when anisole and toluene were blended separately into n-heptane flame. LIF experimental
results indicated that PAH formation was promoted with the addition of anisole and toluene, and the effect of
toluene was stronger than the promotional effect of anisole. The chemical kinetic model predicted the observed
PAH tendencies well in the LIF experiments. Based on this model, reaction pathway and sensitivity analyses were
performed to interpret the chemical effects. Results revealed that, due to their different molecular structures, the
difference in chemical effects between anisole and toluene was notable in PAH growth processes. Anisole
decomposed first via the O-CH3 bond dissociation reaction, and then proceeded to a CO elimination reaction to
yield an important PAH precursor, C5H5, which contributed to PAH formation via styrene and indene reaction
networks. In the toluene added flame, PAH formation was enhanced because of ring expansion reaction on the
dehydrogenated branch of the toluene.

1. Introduction
Because of their high thermal efficiency, long-range, low cost and
convenience [1], internal combustion engines, including diesel and jet
engines and gas turbines, remain the dominant power supply in the
world. But their pollutant emissions–especially soot particles–are one of
the world’s most important challenges, drawing considerable attention
in the past several years [2–4]. Polycyclic aromatic hydrocarbons
(PAHs) are regarded as the precursors of soot particles generated in
incomplete hydrocarbon combustion; due to their carcinogenic, terato­
genic, and mutagenic properties [5–8], both PAHs and soot have dire
consequences to human health, the environment, and climate. Sup­
pressing PAH and soot by the addition of renewable biofuels like alco­
hols [9–11], ethers [12–14], and esters [15–17] is considered a
promising way to alleviate the energy crisis and pollutant emission is­
sues. Various oxygenated biofuels have been used to blend with fossil
fuels for higher thermal efficiency, and to reduce soot and carbon
emissions caused by incomplete combustion [18,19].
One of the main biomass model compounds is anisole, which can be
processed from lignin; many studies have examined its combustion
characteristics, including laminar burning speed [20], flame structure
[21], and chemical kinetics [22–25]. Zare et al. [21] investigated the
laminar burning speed and flame structure of an anisole-air mixture in a
constant volume combustion chamber, and theoretically considered
them in a thermodynamic model. Wagnon et al. [22] developed a
detailed chemical kinetic mechanism for anisole based on measurements
of laminar burning velocities and jet-stirred reactor (JSR) speciation.
Anisole presents good combustion characteristics, but its sooting char­
acteristic seems to be highly sensitive to combustion conditions. Don­
kerbroek et al. [26] studied the effect of ignition delay on soot
production in a heavy-duty diesel engine, fueled by diesel with additives
of some oxygenated fuels. Their results indicated that anisole could be

* Corresponding author.
E-mail address: linhe@sjtu.edu.cn (H. Lin).

https://doi.org/10.1016/j.fuel.2021.121255
Received 16 March 2021; Received in revised form 2 June 2021; Accepted 11 June 2021
Available online 18 June 2021
0016-2361/© 2021 Published by Elsevier Ltd.
Y. Zhang et al.
considered a low sooting candidate fuel, since soot in the exhaust
manifold is non-measurable in anisole blending cases. They attributed
the soot suppression to the exceptionally large, premixed combustion
phase of anisole. However, Londhe et al. [27] tested emission charac­
teristics of a compression ignition engine fueled by diesel and biodiesel
fuels with anisole and methyl acetate as additives, and they suggested
that emission of NOx and soot presents a challenge for anisole blending
combustion.
To better understand anisole addition on soot formation, some
studies focused on the effect of anisole addition on PAH and soot for­
mation in laboratory-scale laminar flames [28–32]. Xiong et al. [28,29]
measured soot volume fraction distributions by time-resolved laser-
induced incandescence (TiRe-LII) and line-of-sight attenuation (LOSA)
techniques in laminar co-flow flames and counterflow flames of n-hep­
tane with various anisole proportions. In both types of flames, they
found that the soot volume fraction increased with a higher anisole
content in the fuel stream; this was attributed to the enhancement of
PAH formation pyrolyzed from anisole during the combustion process.
However, the addition of anisole in co-flow and counterflow con­
figurations changes the flame temperature profile and global equiva­
lence ratio. To reveal the chemical effects of anisole addition on PAH
formation processes, it is important to compare flames with the same
temperature profile, equivalence ratios, and dilution ratios. Further­
more, probing the chemical effect of anisole addition offers more details
about the soot emission of aromatic biofuels.
This study investigates the chemical effect of anisole addition to an n-
heptane flame on PAH formation characteristics. Because of the notable
similarity of molecular structures between toluene and anisole, toluene
was selected as the reference additive; possible dilution and thermal
effects of anisole and toluene additions were avoided by keeping the
temperature profile, dilution ratio, and equivalence ratio the same.
Relative concentrations of PAHs were measured by laser-induced fluo­
rescence (LIF) techniques in laminar premixed flames. A chemical ki­
netic model, coupled with a PAH formation mechanism, was used to
simulate the mole fractions of PAHs and intermediate products, as well
as their rates of production, providing the theoretical details to clarify
the chemical effects of anisole and toluene additions on PAH evolution
in flames.
2. Experimental and computational methods
2.1. Burner and flames
Because it offers stable sooting flames with well-defined boundary
conditions, suitable for modeling, a water-cooled premixed burner with
a stagnation plate was adopted to generate premixed laminar n-heptane
flames at atmospheric pressure in this study. A 5-cm-diameter porous
cylindrical plug installed in the outlet of the burner is used to uniform
the unburned premixed mixture. A stagnation plate was placed at 25 mm
height above the burner (HAB) to stabilize the flame. Flame tempera­
tures at the lower and upper boundaries were controlled by adjusting the
flow rates of cooling water in the burner body and stagnation plate,
which were monitored by two inserted K-type thermocouples,
respectively.
Liquid fuels, n-heptane, anisole, and toluene, were sprayed into an
evaporation chamber using a quartz atomizer (Precision Glassblowing,
Glass Concentric Nebs) with argon, at 0.2 MPa; the sprayed fuels were
then mixed with oxygen and diluted argon in the chamber. The mass
flow rates of the liquid fuels were controlled with a syringe pump
(LSP01-1A), and the gas flow rates were controlled by flowmeters. The
burner, pipelines, and evaporation chamber were preheated to 200 ◦ C,
using electric heating tapes to guarantee vaporization and avoid liquid
fuels condensation. The experimental conditions of the investigated
flames are summarized in Table 1. Anisole and toluene were respectively
blended into n-heptane with 20 vol%. The equivalence ratios and dilu­
tion ratios were kept at 2.3 and 70 vol% throughout the experiments. (In
2
Fuel 303 (2021) 121255
Table 1
Experimental conditions of investigated flames.
Fuels Mass flow rate (g/min) Maximum
temperature
n- anisole toluene O2 Ar
heptane
Tmax (K)
n-heptane 1.20 0 0 1.84 6.48 1768
n-heptane/ 1.00 0.27 0 1.83 6.49 1784
anisole
n-heptane/ 1.00 0 0.23 1.84 6.54 1792
toluene
this equivalence ratio the flames were sooting.) It should be noted that
C/O ratios varied slightly (around 2%) when the equivalent ratios were
kept constant. To exclude the thermal effects of adding anisole and
toluene, maximum flame temperatures were kept nearly constant by
adjusting the total flow rates. When the equivalence ratios, dilution
ratios, and the temperature profiles were fixed, the variation of PAH
formation was, in general, attributed to the chemical effects of anisole
and toluene additions.
Temperature profiles along the flame centerlines were measured
with an S-type fine wire thermocouple. (Details of measurement and
radiation correction procedures have been described in other papers
from this research group [33–35]). Considering the radiation heat loss,
the measured temperatures were corrected using the Shaddix procedure,
with a modified OPPDIF code [36]. The radiation corrected tempera­
tures were averaged from temperatures corrected by the upper (0.3) and
lower (0.6) limits of the coating emissivity [37]; error bands were
calculated from the upper and lower emissivity limits.
2.2. LIF diagnostic system
LIF diagnostic facilities (Fig. 1), are described here only briefly, since
they were applied successfully in previous studies by our group [38–40].
The fourth harmonic (266 nm) of a pulsed Nd: YAG laser (Quantel Q-
smart 850) was used as an excitation source to induce fluorescence
signals of PAHs in flames. The laser frequency and pulse width were 10
Hz and 7 ns, respectively. A 4 mm aperture slot was placed at the central
portion of the laser beam and directed toward the central axis of the
flames. Laser fluence was maintained at around 45 mJ/cm2–a relatively
low energy–to avoid interference from laser-induced incandescence
(LII), but to supply enough signal-to-noise ratio from LIF signals [41,42].
The fluorescence signals were collected by an optical fiber and trans­
mitted into a spectrometer (Princeton SP-2-500i), then recorded by an
ICCD camera (Princeton PI-MAX3) installed at the exit of the spec­
trometer. The gate width of ICCD was set at 50 ns without delay. LIF
signals at different wavelengths were used to distinguish PAH molecules
with different relative sizes, a practice which has been widely adopted in
the literature [43–46]. In this study, the LIF signals between 320 and
360 nm represent the relative concentrations of two and three aromatic
ring species (naphthalene and phenanthrene); the LIF signals between
370 and 410 nm represent the relative concentration of four-aromatic-
ring species (pyrene); LIF signals between 500 and 550 nm represent
the relative concentrations of PAHs with five-member ring structures (a
ring composed of five carbon atoms, acenaphthylene, and fluoranthene).
Basic information regarding the PAHs measured in this study is sum­
marized in Table 2.
2.3. Chemical kinetic model
The chemical kinetic model of the laminar premixed flames was
established using the Chemkin-Pro Software package to analyze the
chemical effects of anisole and toluene. To the best of our knowledge, no
mechanism that included oxidation chemistries n-heptane, anisole, and
toluene and relatively complete PAH formation pathways, has been
covered in the literature. In this study, a reaction mechanism was
Y. Zhang et al. Fuel 303 (2021) 121255

Fig. 1. Schematic diagram of the LIF system.

3. Results and discussion

Table 2
Basic information regarding investigated PAHs.
3.1. Temperature profiles
PAHs Abbreviation Formula Chemical structure

Naphthalene A2 C10H8 Fig. 2 shows temperature profiles along the HAB of the n-heptane, n-
heptane/anisole, and n-heptane/toluene flames, whose maximum flame
Phenanthrene A3 C14H10 temperatures were 1768.2 K, 1783.8 K, and 1791.5 K, respectively, with
around ±70 K error bands. Flame temperatures rapidly reached the
maximum at around 4-mm HAB and remained stable to around 15-mm
Pyrene A4 C16H10 HAB, finally dropping to the temperature of the stagnation plate. The
temperature profiles along the HAB were nearly consistent when anisole
or toluene was blended into the n-heptane. Measuring errors were
Acenaphthylene A2R5 C12H8
mainly attributed to radiation correction, position fluctuation of the
thermocouple, and soot condensation on the thermocouple bead.
Fluoranthene FLTHN C16H10 Despite these unavoidable errors in temperature measurement, the
maximum flame temperatures of the flames were kept nearly constant
because the reactions occurred mainly in the region near the maximum
temperature point. In this way, the influence of flame temperature on
combined, based on a mechanism presented by Yuan et al. [30], which
contained anisole and toluene pyrolysis and PAH formation, and
extended from oxidation chemistry of n-heptane presented by Cai et al.
[47]. The entire mechanism consists of 563 chemical species and 3033
elementary reactions. The reaction mechanism of anisole and toluene in
the mechanism of Yuan et al. was well validated in the reaction flow
experiments, and in the experimental data of some literature, including
laminar premixed flame [48]. The sub-mechanism of n-heptane oxida­
tion has been comprehensively validated in flames [49]. Also, the pre­
dicted PAH results are validated against LIF experiments in the present
work. Consequently, the combined mechanisms in this paper are the
optimal choice for investigation of anisole and toluene addition in n-
heptane flames. The allowed maximum number of grid points, the
allowed maximum gradient, and the curvature between grid points of
the model in Chemkin-Pro were set at 500, 0.2, and 0.5 respectively,
which obtained grid-independent results. Other solver parameters of
this model were set at default values. The measured temperature profiles
were set as the input parameters, without solving the energy equations.

Fig. 2. Measured temperature profiles along HAB of investigated flames.

3
Y. Zhang et al.
PAH formation was excluded and the chemical effects of anisole and
toluene additions were observed in the following experiments.
3.2. Measured and simulated concentrations of PAHs
As mentioned in Section 2.2, absolute concentration of PAHs could
not be obtained using the LIF technique, due to the difficulty of cali­
bration, therefore, the relative amounts of different PAHs were repre­
sented by LIF intensities at three different detection wavelength bands.
The measured LIF signals within the detection wavelength bands of
320–360 nm, 370–410 nm, and 500–550 nm are shown in Fig. 3. In each
wavelength band, LIF signals were normalized by their maximum values
to demonstrate the relative magnitude of PAHs for different fuels. LIF
experimental results before normalization appear in Fig. S1 in the
Supplemental Material. The experimental results showed that relative
concentrations of PAHs with different structures monotonically
increased along the HAB and reached a steady value at around 18-mm
HAB. Compared with the n-heptane flame, the relative concentrations
of all investigated PAHs increased as the anisole blended, and increased
further as the toluene blended, indicating that the chemical effects of
both anisole and toluene promoted PAH formation in n-heptane laminar
Fig. 3. Normalized LIF signals along the centerlines of investigated flames within three detection wavelength bands, 320–360 nm (a), 370–410 nm (b), and 500–550
nm (c).
4
Fuel 303 (2021) 121255
premixed flame, but the effect of toluene in promoting PAH formation
was stronger.
The mole fractions of the investigated PAHs were simulated using the
chemical kinetic model described in Section 2.3. According to the results
from the model, naphthalene (A2), phenanthrene (A3), pyrene (A4),
acenaphthylene (A2R5), and fluoranthene (FLTHN) are the dominant
aromatic species, and their concentrations were much higher than those
of other PAHs. The simulated mole fractions of these PAHs, along the
centerlines of three investigated flames, are shown in Fig. S2 in the
Supplemental Material. To compare with the experimental results, the
simulated mole fractions of A2 + A3 of three flames were normalized,
and to compare with the LIF intensities of 320–360 nm, similarly, A4
was to 370–410 nm, and A2R5 + FLTHN were to 500–550 nm, respec­
tively. The comparison between experimental and model results shown
in Fig. 4 shows very similar concentration profiles of different PAHs
along the HAB; the variation tendencies of these PAHs with anisole and
toluene additions were also consistent.
For better comparison, experimental and simulated PAH mole frac­
tions, reaching stable values after 18-mm HAB, appear in Fig. 5(a) and
(b), respectively. The increased ratios of PAH concentrations with ani­
sole and toluene additions were compared with the n-heptane flame and
Y. Zhang et al. Fuel 303 (2021) 121255

measurement errors and modeling prediction deviations. Overall, the

chemical kinetic model established in this study captured the observed
PAH formation characteristics well. The next section describes its use in
analyzing the chemical effects of anisole and toluene additions.

3.3. Chemical kinetic analysis

Chemical kinetic analysis (including concentration profiles of crucial

intermediates, reaction pathways, and sensitivity coefficients), was
performed to interpret the chemical effects of anisole and toluene ad­
ditions on PAH formation characteristics in n-heptane flames. The re­
action pathway and sensitivity analyses were conducted at positions
where the maximum reaction rates of the investigated reactions were
obtained (near the positions of maximum flame temperatures). It should
be stated that the simulated concentrations of PAHs were affected by
coupling PAH and soot chemistry, but the PAH tendency and the
chemical effects of anisole and toluene additions were barely influenced
and can be analyzed using the chemical kinetic model.

3.3.1. Overview of fuel consumption

The decomposition pathways of n-heptane, anisole, and toluene are
presented to identify the key products and radicals likely to have
participated in the following PAH formation and growth. First, the
decomposition pathways of n-heptane in the three investigated flames
are shown in Fig. 6. The percentages labeled near the arrows represent
ratios of a reactant decomposed by this route and listed in the order of n-
heptane flame, n-heptane/anisole flame, and n-heptane/toluene flame.
The pathways indicated that in the first step, most of the n-heptane
(C7H16) decomposed into four C7H15 radical isomers, and around 20% of
n-heptane decomposed into pentyl radical (C5H11) and ethyl radical
(C2H5). Subsequently, C7H15 radicals and C5H11 radical decomposed via
the unimolecular C–C bond scission and produced small molecule hy­
drocarbons (C2H2, C2H4, C3H6) and radicals (CH3, C2H3, C2H5, C3H5)
with straight-chain structures. In the n-heptane flame, these C1-C3 spe­
cies combined with benzene and grew into larger PAHs. The percentages
of the three flames, labeled in Fig. 6, were relatively close, indicating
that the reaction pathways of n-heptane decomposition were barely
influenced by the anisole or the toluene additions.
Fig. 7 describes the dominant decomposition pathway of anisole and
toluene in anisole/n-heptane flame and toluene/n-heptane flame,
respectively. In addition, the bond dissociation energies of their
branched chains were cited from the literature [50] to clarify the fuel
decomposition. In the overview of anisole decomposition, 93.2% of
anisole was consumed by the O-CH3 bond dissociation reaction forming
phenoxy radical (A1O), and then decomposed into cyclopentadienyl
radical (C5H5) and benzene (A1) through phenol, which could have
contributed to the subsequent formation of PAH. The other A1O was
oxidized and not shown in Fig. 7 (a). At the branched chain of anisole,
the bond dissociation energy of A1–O (99.2 kcal/mol) was stronger than
that of O–CH3 (64.8 kcal/mol), which could account for the first step of
the anisole decomposition. As shown in Fig. 7 (b), toluene decomposed
more easily from C–H bond breaking, leading to benzyl radical (ac­
counting for 77.9%) than by C–C bond breaking, leading to benzene and
methyl (accounting for 12.6%). This is consistent with the bond disso­
Fig. 4. Comparison of simulated (line) mole fraction distribution of A2 + A3
ciation energies involved in toluene. Ethylbenzene (forming through the
(a), A4 (b), A2R5 + FLTHN (c) and measured (scatter) normalized LIF signal
benzyl radical route), as well as benzene, played an important role in the
profiles within three detection wavelength bands, 320–360 nm (a), 370–410
nm (b), and 500–550 nm (c).
PAH formation and growth process of toluene flame.

3.3.2. Formation of incipient ring and growth to PAHs

labeled near the columns. The comparison shown in Fig. 5 indicates that
In this section, the formation and growth pathways of the incipient
the model successfully captured the increasing percentages of PAH
ring, benzene, and five typical PAHs are analyzed and compared among
concentrations observed in experiments with anisole and toluene addi­
the investigated flames. The formation of benzene through small radi­
tions, indicating the reliability of the combined mechanism and the
cals was considered to be the rate-determining step in the larger PAH
chemical kinetic model used in this study. The maximum errors
formation process of hydrocarbon fuels, also, anisole and toluene mol­
observed were from the model results of A2 + A3, which underestimated
ecules contain benzene ring structures. Therefore, the influence of
the experimental results of 320–360 nm, probably attributable to both
adding anisole and toluene on the benzene concentration profiles and

5
Y. Zhang et al. Fuel 303 (2021) 121255

Fig. 5. Maximum PAH mole fractions of experimental results (a) and model results (b) in pure n-heptane flame, n-heptane/anisole flame, and n-heptane/toluene
flame (Percentages labeled near column are increasing ratios with anisole and toluene additions).

Fig. 6. Reaction pathway analysis of n-heptane decomposition in n-heptane flame, n-heptane/anisole flame, and n-heptane/toluene flame (Percentages listed in this
order, and represented ratios decomposing by this route).

formation pathways is the priority to be investigated. As shown in Fig. 8,
the simulated benzene concentration in anisole/n-heptane flame and
toluene/n-heptane flame increased rapidly due to the decomposition
chemistry of anisole and toluene near 1.5-mm HAB, then it quickly
dropped due to the consumption reaction of benzene; finally, the con­
centration reached a constant value after 10-mm HAB among three
flames. In the PAH formation region, the simulated concentration of
benzene in the doping flame was higher than that of the reference n-
heptane flame, which may explain the observed effect of promoting soot
when anisole was added. Fig. 9 depicts formation pathways of benzene
in three flames; the percentage contributions from each route are
labeled in the order of n-heptane flame, n-heptane/anisole flame, and n-
heptane/toluene flame. For n-heptane flame, benzene was generated
mainly from the propargyl (C3H3) recombination reaction, and C5H5
through fulvene. In the flames with anisole and toluene additions, apart
from C5H5 routes, the major pathways leading to the formation of the
benzene were anisole and toluene decompositions, respectively.
Although the decomposition of anisole and toluene produced ben­
zene, the ultimate benzene concentrations were barely changed as a
result of the additions, indicating that the chemical effects of anisole and
toluene on PAH evolution from benzene require further analysis. The
formation pathways of typical PAHs (A2, A3, A4, A2R5, FLTHN) were

6
Y. Zhang et al.
Fig. 7. Decomposition pathway analysis and bond dissociation energies of anisole (a) and toluene (b). (Percentages represent ratios decomposing by this route.)
Fig. 8. Simulated mole fractions of benzene along centerlines of three flames.
subsequently investigated (Fig. 10). For a brief description, some
insignificant reactions and some oxidation reactions were filtered in the
pathway diagram. Note that the reactions of C2 species (especially
acetylene (C2H2)) to these additions were important in PAH growth
processes. Fig. 10 shows that A4 was mainly formed from the A3 radical,
FLTHN was predominantly formed from the reaction of the addition
between A2 and A1/A1-, and A2R5 was produced from A2 species and
indenyl radical (C9H7), which were barely affected by anisole and
toluene additions. A2 and A3 formation were the foundation of the
following PAH evolutions, where the chemical effects of anisole and
toluene were displayed. In toluene/n-heptane flame, toluene directly
participated in PAH formation via the dehydrogenation, hydrogenation,
and addition reactions of its branched chain, increasing A2 and A3
concentrations, as underlining percentages. The chemical effect of ani­
sole also requires further analysis.
7
Fuel 303 (2021) 121255
3.3.3. Sensitivity analysis
To further clarify the chemical effects of anisole and toluene addi­
tions, a sensitivity analysis was conducted using the chemical kinetic
model to highlight some key reactions and intermediates. The sensitivity
coefficients for A2 and A3 mole fractions at the positions that corre­
spond to maximum reaction rates were compared among the three
investigated flames, as shown in Fig. 11. The positive sensitivity co­
efficients of C5H5 formation reactions (R79, R360, R370) indicated the
importance of C5H5 in the PAH formation process. In the n-heptane
flame, C5H5 was formed mainly from the reaction of adding C2H2 and
C3H3 (R360), which were decomposed from n-heptane (described in
Fig. 6). In the n-heptane/anisole flame, C5H5 decomposed mainly from
anisole, as evidenced by the positive sensitivity coefficient of R79:
A1O⇌C5 H5 + CO. It can be seen from Fig. 12 that the simulated con­
centration of C5H5 was highest in the anisole doped flame, followed by
the toluene doped flame. In the n-heptane/toluene flame, PAH forma­
tion processes were more sensitive to the dehydrogenation reaction of
toluene R817 (A1CH2 + H⇌A1CH2 + H2 ), and subsequent C2H2-addi­
tion reaction R1234 (A1CCH2 + C2 H2 ⇌A2 + H), confirming the results
from reaction pathway analysis that toluene directly participated in,
which promoted the PAH formation.
In summary, in the laminar premixed flames investigated, n-heptane
first decomposed into C2 and C3 species; these small molecules and
radicals then generated benzene and C5H5 via reactions to the addition.
Typical PAHs were formed and grew from benzene and C5H5. When
anisole and toluene were blended into n-heptane, the benzene that
decomposed from them promoted PAH formation. Also, because of the
distinction of chemical structures between anisole and toluene, their
chemical effects on promoting PAH formation were quite different.
Anisole decomposed via the O–CH3 bond dissociation reaction and then
formed an important PAH precursor, C5H5, which contributed to the
PAH formation via the indene reaction network and styrene reaction
network. For the toluene added flame, the dehydrogenation, hydroge­
nation, and addition reactions occurring on its branched chain built a
new ring structure, promoting PAH formation.
Y. Zhang et al. Fuel 303 (2021) 121255

Fig. 9. Reaction pathway analysis of benzene formation in n-heptane flame, n-heptane/anisole flame, and n-heptane/toluene flame. (Percentages of decomposition
of three flames listed in this order.)

Fig. 10. Reaction pathway analysis of typical PAHs (A2, A3, A4, A2R5, FLTHN) in n-heptane flame, n-heptane/anisole flame, and n-heptane/toluene flame (Per­
centages of decomposition of three flames were listed in this order.)

8
Y. Zhang et al. Fuel 303 (2021) 121255

(a) Naphthalene (A2)

(b) Phenanthrene (A3)

Fig. 11. Sensitivity coefficients for A2 (a) and A3 (b) mole fractions in three investigated flames.

4. Conclusion

Anisole is a promising renewable biofuel with good combustion

Fig. 12. Simulated mole fractions of C5H5 along centerlines of three investi­
gated flames.
characteristics, but fundamental research into PAH formation of anisole
in flames is quite limited. PAH formation in flame partially fueled by
toluene was compared to that partially fueled by anisole to help clarify
the effects of molecular structure on PAH characteristics. A LIF experi­
ment and a kinetic study were performed to investigate the chemical
effects of anisole and toluene addition on PAH formation in n-heptane-
based laminar premixed flames. The following conclusions can be
drawn:
Experimental results indicated that PAH concentrations mono­
tonically increased with the addition of anisole and toluene, confirming
that PAH formation is promoted by the chemical effects of both anisole
and toluene in n-heptane flame. Furthermore, the effect of toluene in
promoting PAH was stronger than that of anisole. The chemical kinetic
model established in this study accurately predicted the promoting ef­
fects of anisole and toluene on PAH formation characteristics.
In the chemical kinetic analysis, reaction pathway and sensitivity
analyses were performed to interpret the chemical effects of anisole and
toluene on PAH formation. In n-heptane flames, benzene was generated

9
Y. Zhang et al.
mainly from C2 and C3 species which decomposed from n-heptane, while
in anisole and toluene blended flames, benzene originated mainly from
anisole and toluene decomposition. Due to the difference in their mo­
lecular structures, the chemical effects of anisole and toluene were quite
different in the growth processes of PAHs. The addition of the anisole
flame produced C5H5 (an important PAH precursor) from the dissocia­
tion reaction of the anisole molecule. This C5H5 promoted the PAH
formation via styrene and indene reaction networks. For the toluene
addition flame, however, the dehydrogenated toluene participated
directly in the PAH formation by building a new ring structure on its
branched chain and enhancing subsequent PAH formation.
CRediT authorship contribution statement
Yiran Zhang: Writing - original draft, Writing - review & editing,
Investigation, Methodology, Visualization, Formal analysis, Data cura­
tion. Anqi Jiao: Writing - review & editing. Youping Li: Investigation,
Methodology. Peng Liu: Data curation, Methodology, Writing - review
& editing. Guofeng Yang: Methodology, Investigation. Reggie Zhan:
Resources, Supervision. William L. Roberts: Investigation, Writing -
review & editing. Zhen Huang: Resources, Investigation. He Lin:
Project administration, Resources, Supervision, Methodology, Funding
acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was funded by the National Natural Science Foundation of
China (52006142), and the Postdoctoral Research Foundation of China
(2020TQ0187). We gratefully acknowledge the “Island Atmosphere and
Ecology” discipline under the Shanghai Class IV Peak Disciplinary
Development Program.
References
[1] Khalife E, Tabatabaei M, Demirbas A, Aghbashlo M. Impacts of additives on
performance and emission characteristics of diesel engines during steady state
operation. Prog Energy Combust Sci 2017;59:32–78.
[2] Wang Y, Chung SH. Soot formation in laminar counterflow flames. Prog Energy
Combust Sci 2019;74:152–238.
[3] Zhao F, Yang W, Yu W. A progress review of practical soot modelling development
in diesel engine combustion. J Traff Transp Eng (English Edition) 2020;7(3):
269–81.
[4] Gao J, Ma C, Xing S, Sun L, Huang L. A review of fundamental factors affecting
diesel PM oxidation behaviors. Sci China Technol Sci 2018;61(3):330–45.
[5] Tongo I, Ogbeide O, Ezemonye L. Human health risk assessment of polycyclic
aromatic hydrocarbons (PAHs) in smoked fish species from markets in Southern
Nigeria. Toxicol Rep 2017;4:55–61.
[6] Amador-Muñoz O, Martínez-Domínguez YM, Gómez-Arroyo S, Peralta O. Current
situation of polycyclic aromatic hydrocarbons (PAH) in PM2.5 in a receptor site in
Mexico City and estimation of carcinogenic PAH by combining non-real-time and
real-time measurement techniques. Science of The Total Environment 2020;703:
134526.
[7] Kennedy IM. The health effects of combustion-generated aerosols. Proc Combust
Inst 2007;31(2):2757–70.
[8] Finlayson-Pitts BJ. Tropospheric air pollution: ozone, airborne toxics, polycyclic
aromatic hydrocarbons, and particles. Science 1997.
[9] Zhang Y, Li Y, Liu P, Zhan R, Huang Z, Lin H. Investigation on the chemical effects
of dimethyl ether and ethanol additions on PAH formation in laminar premixed
ethylene flames. Fuel 2019;256:115809.
[10] Yan F, Xu L, Wang Y, Park S, Sarathy SM, Chung SH. On the opposing effects of
methanol and ethanol addition on PAH and soot formation in ethylene counterflow
diffusion flames. Combust Flame 2019;202:228–42.
[11] Liu H, Wang X, Wu Y, Zhang X, Jin C, Zheng Z. Effect of diesel/PODE/ethanol
blends on combustion and emissions of a heavy duty diesel engine. Fuel 2019;257:
116064.
[12] Li Z, Amin HMF, Liu P, Wang Y, Chung SH, Roberts WL. Effect of dimethyl ether
(DME) addition on sooting limits in counterflow diffusion flames of ethylene at
elevated pressures. Combust Flame 2018;197:463–70.
10
Fuel 303 (2021) 121255
[13] Cai L, vom Lehn F, Pitsch H. Higher alcohol and ether biofuels for compression-
ignition engine application: a review with emphasis on combustion kinetics.
Energy Fuels 2021;35(3):1890–917.
[14] Uslu S, Aydın M. Effect of operating parameters on performance and emissions of a
diesel engine fueled with ternary blends of palm oil biodiesel/diethyl ether/diesel
by Taguchi method. Fuel 2020;275:117978.
[15] Bolonio D, García-Martínez M-J, Ortega MF, Lapuerta M, Rodríguez-Fernández J,
Canoira L. Fatty acid ethyl esters (FAEEs) obtained from grapeseed oil: a fully
renewable biofuel. Renewable Energy 2019;132:278–83.
[16] Srivastava PK, Verma M. Methyl ester of karanja oil as an alternative renewable
source energy. Fuel 2008;87(8):1673–7.
[17] Likhanov VA, Lopatin OP, Yurlov AS. Biofuel based on methanol and methyl ester
of rapeseed oil for diesel engine. IOP Conf Series: Mater Sci Eng 2020;734:012208.
[18] Jiaqiang E, Pham M, Zhao D, Deng Y, Le D, Zuo W, et al. Effect of different
technologies on combustion and emissions of the diesel engine fueled with
biodiesel: a review. Renew Sustain Energy Rev 2017;80:620–47.
[19] Mohd Noor CW, Noor MM, Mamat R. Biodiesel as alternative fuel for marine diesel
engine applications: a review. Renew Sustain Energy Rev 2018;94:127–42.
[20] Wu Y, Rossow B, Modica V, Yu X, Wu L, Grisch F. Laminar flame speed of
lignocellulosic biomass-derived oxygenates and blends of gasoline/oxygenates.
Fuel 2017;202:572–82.
[21] Zare S, Roy S, El Maadi A, Askari O. An investigation on laminar burning speed and
flame structure of anisole-air mixture. Fuel 2019;244:120–31.
[22] Wagnon SW, Thion S, Nilsson EJK, Mehl M, Serinyel Z, Zhang K, et al.
Experimental and modeling studies of a biofuel surrogate compound: laminar
burning velocities and jet-stirred reactor measurements of anisole. Combust Flame
2018;189:325–36.
[23] Friderichsen AV, Shin E-J, Evans RJ, Nimlos MR, Dayton DC, Ellison GB. The
pyrolysis of anisole (C6H5OCH3) using a hyperthermal nozzle. Fuel 2001;80(12):
1747–55.
[24] Arends IWCE, Louw R, Mulder P. Kinetic study of the thermolysis of anisole in a
hydrogen atmosphere. J Phys Chem 1993;97(30):7914–25.
[25] Hemings EB, Bozzano G, Dente M, Ranzi E. Detailed kinetics of the pyrolysis and
oxidation of anisole. 10th International Conference on Chemical and Process
Engineering. 2011.
[26] Donkerbroek AJ, Boot MD, Luijten CCM, Dam NJ, ter Meulen JJ. Flame lift-off
length and soot production of oxygenated fuels in relation with ignition delay in a
DI heavy-duty diesel engine. Combust Flame 2011;158(3):525–38.
[27] Londhe H, Luo G, Park S, Kelley SS, Fang T. Testing of anisole and methyl acetate
as additives to diesel and biodiesel fuels in a compression ignition engine. Fuel
2019;246:79–92.
[28] Xiong G, Boot M, Zhou L, Reijnders J, De Goey P. Soot particle size distribution
measurements in laminar diffusion flames of n-heptane with oxygenated aromatic
fuel additives by time-resolved laser-induced incandescence. Energy Fuels 2018;32
(11):11511–8.
[29] Xiong G, Xie J, Chen L, Wang W, Zhou L. Sooting tendency of n-heptane/anisole
blends in laminar counter-flow flames with oxygen enrichment. Fuel 2019;255:
115820.
[30] Yuan W, Li T, Li Y, Zeng M, Zhang Y, Zou J, et al. Experimental and kinetic
modeling investigation on anisole pyrolysis: implications on phenoxy and
cyclopentadienyl chemistry. Combust Flame 2019;201:187–99.
[31] Nowakowska M, Herbinet O, Dufour A, Glaude P-A. Detailed kinetic study of
anisole pyrolysis and oxidation to understand tar formation during biomass
combustion and gasification. Combust Flame 2014;161(6):1474–88.
[32] Scheer AM, Mukarakate C, Robichaud DJ, Ellison GB, Nimlos MR. Radical
chemistry in the thermal decomposition of anisole and deuterated anisoles: an
investigation of aromatic growth. J Phys Chem A 2010;114(34):9043–56.
[33] Lin B, Gu H, Ni H, Guan B, Li Z, Han D, et al. Size distribution of soot particles in
premixed n-heptane and methylcyclohexane flames. Energy Fuels 2018;32(3):
3883–90.
[34] Lin B, Gu H, Guan B, Han D, Gu C, Huang Z, et al. Size evolution of soot particles
from gasoline and n-heptane/toluene blend in a burner stabilized stagnation flame.
Fuel 2017;203:135–44.
[35] Lin B, Gu H, Ni H, Guan B, Li Z, Han D, et al. Effect of mixing methane, ethane,
propane and ethylene on the soot particle size distribution in a premixed propene
flame. Combust Flame 2018;193:54–60.
[36] Smooke MD, Puri IK, Seshadri K. A comparison between numerical calculations
and experimental measurements of the structure of a counterflow diffusion flame
burning diluted methane in diluted air. Symp (Int) Combust 1988;21(1):1783–92.
[37] Peterson RC, Laurendeau NM. The emittance of yttrium-beryllium oxide
thermocouple coating. Combust Flame 1985;60(3):279–84.
[38] Li Y, Zhang Y, Zhan R, Huang Z, Lin H. Effects of ammonia addition on PAH
formation in laminar premixed ethylene flames based on laser-induced
fluorescence measurement. Energy 2020;213:118868.
[39] Li Y, Zhang Y, Zhan R, Huang Z, Lin H. Study of PAH formation in laminar
premixed toluene and C8H10 aromatics flames. Fuel 2020;275:117774.
[40] Li Y, Zhang Y, Zhan R, Huang Z, Lin H. Experimental and kinetic modeling study of
ammonia addition on PAH characteristics in premixed n-heptane flames. Fuel
Process Technol 2021;214:106682.
[41] Bejaoui S, Mercier X, Desgroux P, Therssen E. Laser induced fluorescence
spectroscopy of aromatic species produced in atmospheric sooting flames using UV
and visible excitation wavelengths. Combust Flame 2014;161(10):2479–91.
[42] Liu P, Zhang Y, Wang L, Tian B, Guan B, Han D, et al. Chemical mechanism of
exhaust gas recirculation on polycyclic aromatic hydrocarbons formation based on
laser-induced fluorescence measurement. Energy Fuels 2018;32(6):7112–24.
Y. Zhang et al.
[43] Lee SM, Yoon SS, Chung SH. Synergistic effect on soot formation in counterflow
diffusion flames of ethylene–propane mixtures with benzene addition. Combust
Flame 2004;136(4):493–500.
[44] Yoon SS, Lee SM, Chung SH. Effect of mixing methane, ethane, propane, and
propene on the synergistic effect of PAH and soot formation in ethylene-base
counterflow diffusion flames. Proc Combust Inst 2005;30(1):1417–24.
[45] Chen B, Liu X, Liu H, Wang H, Kyritsis DC, Yao M. Soot reduction effects of the
addition of four butanol isomers on partially premixed flames of diesel surrogates.
Combust Flame 2017;177:123–36.
[46] Singh P, Sung C-J. PAH formation in counterflow non-premixed flames of butane
and butanol isomers. Combust Flame 2016;170:91–110.
11
Fuel 303 (2021) 121255
[47] Cai L, Ramalingam A, Minwegen H, Alexander Heufer K, Pitsch H. Impact of
exhaust gas recirculation on ignition delay times of gasoline fuel: an experimental
and modeling study. Proc Combust Inst 2019;37(1):639–47.
[48] Bierkandt T, Hemberger P, Oßwald P, Krüger D, Köhler M, Kasper T. Flame
structure of laminar premixed anisole flames investigated by photoionization mass
spectrometry and photoelectron spectroscopy. Proc Combust Inst 2019;37(2):
1579–87.
[49] Wullenkord J, Graf I, Baroncelli M, Felsmann D, Cai L, Pitsch H, et al. Laminar
premixed and non-premixed flame investigation on the influence of dimethyl ether
addition on n-heptane combustion. Combust Flame 2020;212:323–36.
[50] Luo Y-R. Handbook of bond dissociation energies in organic compounds. CRC
Press; 2002.